Parasiticidal compositions of olefins and perchloromethyl mercaptan



Patented May 22, 1951 PARASITICHDAL COMPOSITIONS F OLE- FINS ANDPERCHLOROMETHYL MER- (JAP'EAN Delaware No Drawing. Application October21, 1948, Serial No. 55,835

8 Claims.

This invention relates to new and useful improvements in parasiticidalpreparations and more particularlyto improved fungicides andinsecticides. This invention relates also to methods of protectingorganic material subject to attack by low orders of organisms.

It has now been found that organic thio trichloromethanes, derived fromthe reaction of unsaturated organic compounds and perchloromethylmercaptan and their derivatives, are extremely eifective for destroyingor checking the growth of "bacteria, fungi and insects. These compoundsmay be used as novel ingredients of seed and plant protec'tants becauseof their disinfecting action on soil containing harmful orgam'sms.

These compounds may also be applied to parent materials to retard orprevent fungus growth and mildew formation. Some of the parent matectivepurposes are leather, wood, fur, wool,

coated'fabrics and other substances.

These compounds which are in most cases liquid, may beapplied as a dustmixed with a solid powder, such as clay, talc and bentonite. They mayalso be applied as a spray in a liquid carrier, either as a solution ina solvent, or as a suspension or emulsion in a non-solvent, such aswater. When applied as a spray in water, it may be desirable toincorporate wetting agents and/or emulsifiers.

The water-soluble wetting agents and emulsifiers that may be usedcomprise the sulfates of long chain alcohols such as dodecanol up tooctadecanol, sulfonated amide and ester derivatives, sulfonated aromaticand mixed alkyl-aryl sulfonate derivatives, esters of fatty acids suchas ricinoleic acid ester of sorbitol and petroleum sulfonates of C10 toC20 length. The non-ionic emulsifying agents such as the ethylene oxideproducts of alkylated phenols may also be used. It is to be understoodthat these and similar compounds are intended when the term wettingagent is used hereafter.

By virtue of their solubility in the volatile Freons i. e., CC13F,CC12F2, CClFs, CI-ICl2F, etc,

and other aerosol type solvents together with positions for :space sprayand fumigation applications. When put up in this form they can bedispensed in the conventional pressure containers known in the art. Theycan be of course be volatilized by application of heat in the area to befumigated. The compounds of this invention, because of their volatility,are adapted for dispersion in other normally volatile solvents such asalcohols, ethers and hydrocarbons boiling below the initial boilingpoint of kerosene.

The compounds of this invention are readily compatible with otherinsecticidal and fungicidal mixtures and possesses a high degree ofchemical stability in the atmosphere which makes them ideally suitablefor use as agricultural spray residues. They may therefore be admixedwith carriers that are themselves active such as other parasiticides,hormones, herbicides, fertilizers and stomach and contact insecticidessuch as the arsenates, fluorides, rotenone and the various fish poisonsand organic insecticides such as di(p-) chlorophenyl -trichloroethane,benzene-hexachloride and similar products may also be advantageouslyadded.

The thio trichloromethanes of this invention may be prepared by theassociation and condensation reactions of perchloromethyl mercaptan withan unsaturated compound such as, for example, alkenes, alkenederivatives, aromatic compounds and aromatic derivates. These reactionsmay be carried out with or without a catalyst and at varyingtemperatures depending upon the nature of the unsaturated reactant andthe stability of the desired products. For most unsaturated compounds areaction temperature of -120 C. is preferable.

The unsaturated compounds used in this reaction may be primary,secondary or tertiary.

They may be attached to organic groupscontaining a variety ofsubstituents such as ethers, acids, halides, esters, aromatic nucleiwhich in turn may be substituted, cyclic aliphatic groups and the like.

The general reaction may be written as follows:

Equation 1 It should be borne in mind, that while the formulae forparticular compounds indicated below represent the best availableinformation as to the structure of the major compound formed by thereactions indicated, the addition of the Cl and S0013 components ofperchloromethyl mercaptan to the unsaturated compounds also proceeds tosome extent in the manner indicated in Equation II below, as compared toEquation I above, and the reaction product may therefore be a mixture ofisomers.

Equation II The examples given below of the parasiticidal activity ofthe compounds of this invention are therefore expressed in terms of theproducts of the particular reactants.

The following examples are given to illustrate this invention andinclude both the preparation of these compounds and test resultsobtained by their uses for the stated purpose.

EXAMPLE I Reaction of perchloro'methyl mercaptan with octene-Z 123 g.(1.1 mols) of octene-l and 186 g. (1 mol) of perchloromethyl mercaptanwere charged to a 500 cc. Erlenmeyer flask and heated on the steam bathto 90-95 C. for 24 hours. The reaction mixture was then distilled underreduced pressure from a Claisen distilling flask with the followingresults:

- Wei ht DlStlHillllOIl Pressure [action Temperature (ads) 523 Mm. GramsUp to 115 C 4 107 115125 C 24 182 Residue l3 F I consisted primary ofunreacted perchloromethyl mercaptan and octene-l. The major portion of FII distilled over at 119-121 C. at 2 mm. pressure. The analysis of F IIis as follows:

Per Cent Per Cent Per Cent Per Cent .0 H S C1 Found F H 36 47 5 29 11.08 48.11 Theory for- H CsH13(S3CH2C1. 36. 24 5.37 10. 74 47.65

EXAMPLE 11 Reaction of perchlo'romethyl mercaptan with butadiene dimer(vinyl cycloheasene) 108 g. of butadiene dimer (vinyl cyclohexene) and372 g. of perchloromethyl mercaptan were mixed and heated to 92-99" C.for 18 hours. The reaction mixture was then charged to a Claisendistilling flask and an attempt made to distill the product. 110 g.distilled over below 100 C. at 2 mm pressure but on heating to a pottemperature of 170 C. evidence of slight decomposi= tion was noted andthe distillation was discontinued. The residue consisted of 345; g. of areddish viscous oilhaving'a faint sharp odor.

It is apparent from the amount of high boiling residue recovered and theanalysis of the residue that the product consists of a mixture of monoand ell-substituted vinyl cyclohexene.

EXAMPLE III Reaction of perchloromethyl mercaptan with dz'isobutylene112 g. of diisobutylene and 186 g. of perchloramethyl mercaptan weremixed and heated to -99 C. for 2 1 hours. On distillation it was foundthat very little reaction had taken place. The mixture was again heatedto the same temperature for an additional 42 hours. On distillation froma Claisen flask the following fractions were obtained:

Fraction Boiling Range Weight Recovered F I below 80 C. 180 mm. 89 g.(diisobutylene).

F II 80 C 180 mm. to 72 g. (mostly per- C. 10 mm. chloro methylmercaptan).

FIII 72 O.@10mml to 88 0. 9g.

F IV 88-98 C. 2 mm 19 g.

FV Residue 10 g.

Analysis of fractions IV and V gave the following results:

Per Cent Per Cent Per Cent Per Cent C H S Cl F IV 23. 4O 2. 55 17 16 60.74 F V 36. l0 5. 28 12. 42 47. 92 Theory for-- (111 (EH3CHa(i3GHz(fCH2Cl 36. 24 5.37 10. 74 47.65

C H SI Theory for-- (13113 CHx-C s c on 24. so s. 08 13.17 57 61 C H2ClF IV From the analysis itappears thatj ,IVislargely the addition productof perchloromethyl mercaptan and isobutylene whereas F V is the additionproduct with diisobutylene.

colorless oildistilling over at I'm-117 C.@ 3m n.

pressure.

Analysis of this fraction gave-the following results:

EXAMPLE IV Per Cent Per Cent PerCent Percent Reaction of perchloromethylmercaptcm with allyl O H 01 S ether Found 25.19 2.89 to. 12 12.60 Amixtureconsisting of.50 g. of allyl ether and 186 g. of perchloromethylmercaptan after heat- 0 ing to 92-96 C. for 22 hours gave the followingCH3(|l/ 0CH2OHOHzC] 17 2'80 49 65 1120 results on distillation;

SCCls F t' B '1' R 6 vhleight mo lon 01 mg ange eerceoiv- EXAMPLE VIGrams The results of laboratory insecticide and fungi- Up to109-O.@2mm..-. 71 cide tests on these compounds are given in the Z;table below. The values given under immersion Rcsldue 68 test representthe mortality of the test insect after 96l1ours following a 2 minuteimmersion Analysis of fractions 11 and IV gave the following results:

in an 0.25% aqueous dispersion of the test compound. The results of theinjection test are The analysis indicates that F 11 consists chiefly ofthe mono addition product whereas F IV isa mixture of the mono and diaddition compounds.

EXANIPLE V Reaction 0 perchZoromethg Z mercaptan with allyl acetate Amixture of 50 g. of allyl acetate and 93 g. of perchloromethyl mercaptanafter heating at 92- 95" C. for 44 hours was distilled giving 46 g. of agiven as per cent mortality 96 hours following injection of 0.5 mg. ofthe test compound per gram of insect body Weight. The slide germinationtechnique for fungicidal testing was carried out as described by Wellmanand McCallan (Contributions of Boyce Thompson Institute, vol. 13, No. 3,pages 171-176). The results are reported as the minimum concentration,expressed as weight percent, giving 50% inhibition of spore germination.

Insecticidal Data Funggcidalpatta, Slide ermma 10o Immersion Test Ini jection Test, Compound Reaction Product of H J perchloromethyl mercaptanand .imencana Blattella Omelpeltos fig g germanica socintus c AlternariaSclerotinia (German) (Mllkweed) solani fructicola Roach Bug 4 MaleFemale Octene-l 100 100 40 40 0. 01 0. 001 0.01 0. 001 Tetradecenel. 20100 40 80 0. 1 0. 01 0. 1 0. 01 Isobutylene... 100 100 80 100 0.001 0.001 0. 001-0. 0001 Diisobutylene.-. 100 100 100 100 0.01 0. 001 0.001-0. 0001 Vinyl cyclohexene 50 80 40 0. 01 0. 001 0. 01 0. 001 Allylether (mono substituted)... 100 100 40 80 0.01 0. 601 0.01 0. 001 Allylether (Disubstituted)...-.. 30 100 0.01 0. 001 0.01 O. 001 AllylAcetate. 100 100 100 0.0001 0.01 0. 001 Undecylemc Acid 100 100 60 1000.01 0. 001 0.01 *0. 001

It is apparent that mixtures of the various compounds synthesized alsopossess the indicated parasiticidal activity.

This invention has been described with respect to specific embodimentsbut it is not to be limited thereby.

What is claimed is:

1. A parasiticidal dust composition comprising the reaction product ofan unsaturated organic compound selected from the group consisting ofaliphatic and alicyclic organic compounds and perchloromethyl mercaptanas the active ingredient admixed with a powdered clay.

2. A parasitioidal dust composition as in claim 1 in which the clay isbentonite.

3. A parasiticidal composition comprising the reaction product of anunsaturated organic compound selected from the group consisting ofaliphatic and alicyclic organic compounds and per chloromethyl mercaptanas the active ingredient admixed with a solid, powdered, inert diluent.

4 A parasiticidal dust composition as in claim 1 in which theunsaturated organic compound is allyl acetate.

5. A parasiticidal dust composition as in claim 1 in which theunsaturated organic compound is undecylenic acid.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,197,781 Badertscher et a1. Apr.23, 1940 2,319,183 Badertscher et al. May 11, 1943 OTHER REFERENCESRcark et al.; U. S. D. A. Technical Bulletin No. 162, March 1929,entitled Tests of Various Aliphatic Compounds as Fumigants, page 33.

1. A PARASITICIDAL DUST COMPOSITION COMPRISING THE REACTION PRODUCT OFAN UNSATURATED ORGANIC COMPOUND SELECTED FROM THE GROUP CONSISTING OFALIPHATIC AND ALICYLIC ORGANIC COMPOUNDS AND PERCHLOROMETHYL MERCAPTANAS THE ACTIVE INGREDIENT ADMIXED WITH A POWDERED CLAY.